The present invention relates to quantitative analytic sensors. More specifically the present invention relates to a sensor that uses an electrode response to measure the concentration of free chlorine in a solution.
Chlorine, in one form or another, is often used as a disinfectant for the treatment of water. Such treatment can include disinfecting drinking water, treating swimming pools, disinfecting articles that come into contact with water, and many other applications in which it is desirable to kill bacteria in water. Proper operation of water disinfectant systems generally requires the measurement of chlorine in order to ensure that a sufficient amount of chlorine has been used.
Free chlorine is chlorine in one or more forms that are useful as disinfectants. Free chlorine can exist as dissociated chlorine gas, hypochlorite ion, and hypoclorous acid. The relative ratio of hypochlorite ion to hypoclorous acid is known to be related to the pH of the solution. Rosemount Analytical Incorporated, an Emerson Process Management Company, provides a free chlorine sensor for the continuous determination of free chlorine, under the trade designation model 499ACL-01. The sensor can measure free chlorine in samples having pH as high as 9.5 and operates as an amperometric sensor.
In general, prior art free chlorine sensors needed to be paired with some form of pH compensation. Compensation of the pH was necessary because only the hypoclorous acid form of free chlorine is reducible at the cathode of an amperometric device. As set forth above, free chlorine exists in two forms in solutions: hypochlorite ion and hypoclorous acid with the relative ratio of the two being dependent upon the pH of the solution. Below pH 6, free chlorine is effectively 100% hypoclorous acid, while above pH 10, free chlorine is effectively 100% hypochlorite ion. The relative concentrations of hypochlorite ion and hypochlorous acid varying with pH as illustrated in FIG. 1.
It would be extremely useful if free chlorine sensing could be done without the additional sensing of pH. The current state of the art wherein pH must be sensed or known to some degree unnecessarily complicates free chlorine measurement and increases the expense of measurement systems.
Attempts have been made to mitigate the effects of varying pH on chlorine measurements. For example, buffers have been used in order to attempt to maintain the internal electrolyte solution at a selected pH. Further, U.S. Pat. No. 5,693,204 to Popp provides passive pH adjustment for analytical instruments. However, attempts, to date, involved cumbersome pH maintenance systems or independent pH compensation for the chlorine measurement. The provision of a free chlorine sensor that would not require pH measurement and compensation, as well as the provision of a simple and easily serviced free chlorine sensor would advance the art of free chlorine sensing and lower overall costs for providing and maintaining water disinfectant systems.